Reduction of symmetrical intramolecular diarylmethyl ethers (3a and 8a) and amines (3b and 8b) with alkali metals in THF allows the generation of unsymmetrical oxy-or amino- functionalised arylmethyl organometallics. Such intermediates were successfully trapped with various electrophiles, allowing a new access to unsymmetrically 2, 2′-disubstituted-1, 1′-biaryls (5aa–5bf) and 1, 8-disubstituted naphthalenes (10aa–10be).